Addition-fragmentation oligomers having high refractive index groups

Patent metadata

Field	Value
Publication number	US-2016346170-A1
Application number	US-201515112220-A
Country	US
Kind code	A1
Filing date	Feb 10, 2015
Priority date	Feb 18, 2014
Publication date	Dec 1, 2016
Grant date	—

Abstract

Addition-fragmentation oligomers of the general formula Z—B y -A-(B-A) x -B-A-B y —Z, where the A monomers units are derived from a diester or diacid, the B monomer units are derived from a difunctional monomer having functional groups co-reactive with the acid or ester groups of the A monomer, x+y is zero to 60, Z comprises an ethylenically unsaturated, polymerizable group, A monomers comprise a 1-methylene-3,3-dimethylpropyl group, and at least one B monomer unit comprises a high refractive index group.

First claim

1 . An addition-fragmentation oligomer of the formula

wherein
R A is

R B a (hetero)hydrocarbyl group, wherein at least one R B is substituted with a high refractive index group,
X 1 is —O— or NR 5 —, where R 5 is H or C 1 -C 4 alkyl;
Z comprises an ethylenically unsaturated polymerizable group;
y is 0 or 1;
x is 0 or 1.

2 . The addition-fragmentation oligomer of claim 1 , wherein at least 50% of the R B units are substituted by a high refractive index group.

3 . The addition-fragmentation oligomer of claim 1 , wherein at least 75% of the R B units are substituted by a high refractive index group.

4 . The addition-fragmentation oligomer of claim 1 , wherein the high refractive index group is selected from benzyl, 2-, 3-, and 4-biphenyl, 1-, 2, 3-, 4-, and 9-fluorenyl, 4-(1-methyl-1-phenethyl)phenoxyethyl; phenylthio; 1-, 2-, 3- and 4-napthyl, 1- and 2-naphthylthio; 2,4,6-tribromophenoxy; 2,4-dibromophenoxy; 2-bromophenoxy; 1-, and 2-naphthyloxy; 3-phenoxy-; 2-, 3- and 4-phenylphenoxy; 2,4-dibromo-6-sec-butylphenyl; 2,4-dibromo-6-isopropylphenyl; 2,4-dibromophenyl; pentabromobenzyl and pentabromophenyl.

5 . The addition-fragmentation oligomer of claim 1 wherein Z comprises a (meth)acrylate or vinyl group.

6 . The addition-fragmentation oligomer of claim 1 derived from A compounds of the formula:
R 1 —O—CO—R A —CO—O—R 1 , wherein R A is a 1-methylene-3,3-dimethylpropyl group and R 1 is H, alkyl, aryl or R FG , where R FG is an aryl or an alkyl further substituted with a nucleophilic or electrophilic functional group.

7 . The addition-fragmentation oligomer of claim 6 derived from B compounds of the formula:
X 2 —R B —X 2 , wherein R B is a (hetero)hydrocarbyl group and X 2 is functional group reactive with the functional groups of the A compound.

8 . The addition-fragmentation oligomer of claim 7 wherein the compound of the formula X 2 —R B —X 2 is selected from difunctional epoxides, diols, aziridines, isocyanates and diamines.

9 . The addition fragmentation of claim 7 where reaction between the A compounds and B compounds yields an intermediate oligomer of the formula:
A and B compounds may have the structure

wherein
R A is

R B a (hetero)hydrocarbyl group, wherein at least one R B contains a high refractive index group,
X 1 is —O— or NR 5 —, where R 5 is H or C 1 -C 4 alkyl;
Z comprises an ethylenically unsaturated polymerizable group;
X 5 is a terminal functional group selected from —OR 1 of the A compounds or X 2 of the B compounds;
y is 0 or 1;
x is 0 or 1.

10 . The addition-fragmentation oligomer of claim 1 where y is 1.

11 . The addition-fragmentation oligomer of claim 1 where y is 0.

12 . The addition-fragmentation oligomer of claim 1 where x+y is 0 to 60.

13 . The addition-fragmentation oligomer of claim 1 where x+y is 1 to 20.

14 . The addition-fragmentation oligomer of claim 9 where the Z group is derived from an ethylenically unsaturated compound of the formula:
(Z) d —X 3 , where Z comprises an ethylenically unsaturated group, and X 3 is a functional group reactive with the terminal functional groups of the intermediate oligomer.

15 . The addition-fragmentation oligomer of claim 14 wherein the compound of the formula (Z) d —X 3 is of the formula:
Y 1 —R 3 —O—CO—CR 2 ═CH 2 , where Y 1 is an electrophilic functional group reactive with terminal electrophilic functional groups of the intermediate oligomer, R 3 is an alkylene, R 2 is H or CH 3 .

16 . The addition-fragmentation oligomer of claim 14 wherein the compound of the formula (Z) d —X 3 is of the formula:
Y 2 —R 3 —O—CO—CR 2 ═CH 2 , where Y 2 is an nucleophilic functional group reactive with the electrophilic functional groups of the intermediate oligomer, R 3 is an alkylene, R 2 is H or CH 3 .

17 . The addition-fragmentation oligomer of claim 9 wherein the high refractive index group is derived from a compound of the formula: (R RI ) d —X 5 ,
where R RI comprises high refractive index group,
X 5 is a reactive functional group, and subscript d is at least 1.

18 . A polymerizable composition comprising the addition-fragmentation oligomer of any of claims 1 - 17 , at least one free-radically polymerizable monomer, and an initiator.

19 . The polymerizable composition of claim 18 comprising:
a) 85 to 100 parts by weight of an (meth)acrylic acid ester;
b) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer;
c) 0 to 10 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer;
d) 0 to 5 parts vinyl monomer; and
e) 0 to 100 parts of a multifunctional (meth)acrylate; based on 100 parts by weight total monomer a) to d), and
f) 0.1 to 12 parts by weight of the addition-fragmentation oligomer, based on 100 parts by weight of a) to e), and
g) an initiator.

20 . The polymerizable composition of claim 19 further comprising 0.01 to 100 parts of a multifunctional (meth)acrylate.

21 . The polymerizable composition of claims 18 to 20 comprising a photoinitiator.

22 . The polymerizable composition of any of claims 18 to 20 wherein the initiator is a thermal initiator.

23 . The polymerizable composition of any of claims 18 to 22 containing less than 0.01 wt. % cobalt compounds.

24 . The polymerizable composition of any of claims 18 - 23 further comprising an inorganic filler.

25 . The polymerizable composition of claim 24 wherein the filler is a surface-modified silica filler.

26 . An article comprising a layer of the polymerizable composition of any of claims 18 - 25 on a substrate.

27 . An article comprising the cured polymerizable composition of any of claims 18 - 25 on a substrate.

28 . A method of bonding two substrates together comprising the steps of coating the polymerizable composition of any of claims 18 - 25 to a surface of one or both substrates, contacting the coated surfaces, optionally with pressure, and curing the polymerizable compositions.

29 . A method of bonding two substrates together comprising the steps of coating the polymerizable composition of any of claims 18 - 25 to a surface of one or both substrates, wherein the coating of polymerizable composition is at least partially cured, contacting the coated surfaces optionally with pressure, and further curing the polymerizable compositions if necessary.

30 . A hardcoat composition comprising one or more multifunctional (meth)acrylate monomers or (meth)acrylate oligomers, and the addition-fragmentation oligomer of any of claims 1 to 12 .

31 . The hardcoat composition of claim 30 comprising:
a) 0.1-10 wt. % of the addition fragmentation oligomer;
b) 20-80 wt. % of multifunctional (meth)acrylate monomers and/or multifunctional (meth)acrylate oligom

Assignees

• 3M Innovative Properties Co

Inventors

• Fornof Ann R
• Moser William H
• Joly Guy D

Classifications

• A61K6/871

  Quartz; SiO2 · CPC title

• A61K6/889

  Polycarboxylate cements; Glass ionomer cements · CPC title

• C09J4/06 Primary

  {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00 · CPC title

• A61K6/878

  Zirconium oxide · CPC title

• A61K6/16

  Refractive index · CPC title